TWI895271B - Photosensitive resin composition - Google Patents

Abstract

The present invention is to provide a cured film for use in liquid crystal display devices, organic EL display devices, and the like. The photosensitive resin composition of the present invention provides the cured film with high lyophilicity, thereby suppressing uneven coating of overlying materials applied using inkjet or slit coating methods. The present invention addresses this problem with a photosensitive resin composition suitable for use as the first bank material in display devices that define individual pixels by forming first and second banks directly on a substrate or through other layers. The composition comprises the following components: (A), (B), (C), and (D): (A) alkali-soluble resin, (B) fluorine-containing thermally decomposable polymer, (C) solvent, and (D) photosensitive agent.

Description

Photosensitive resin composition

The present invention relates to a photosensitive resin composition and a cured film obtained therefrom. More specifically, the present invention relates to a photosensitive resin composition capable of forming a highly liquid-repellent image on the surface of the cured film, a cured film thereof, and various materials using the cured film. This photosensitive resin composition is particularly suitable for use as an interlayer insulating film in liquid crystal displays or electroluminescent displays, as a light-shielding material for inkjet printing, or as a partition material.

In recent years, the use of inkjet technology to manufacture full-color display substrates in the manufacturing of display devices such as thin-film transistor (TFT) liquid crystal displays (LCDs) and organic electroluminescent devices has been actively studied. For example, regarding the production of color filters for LCDs, proposals have been made to utilize conventional printing, electrodeposition, dyeing, or pigment dispersion methods. These methods utilize a light-shielding photosensitive resin layer to form areas defining pre-patterned pixels (hereinafter referred to as banks), and then deposit ink droplets within the areas enclosed by these banks. These color filters and their manufacturing methods (Patent Document 1) are also being proposed. However, the inkjet method suffers from issues such as uneven film thickness due to insufficient discharge stability. Therefore, Patent Document 2 proposes using multiple parallel partitions and plate-like members to prevent ink flow to partition pixels and prevent uneven film thickness (Patent Document 2). Another proposal is to use two types of banks arranged in a grid pattern to suppress color mixing during ink application, enabling a display with high color purity (Patent Document 3). However, when ink is applied to these partitions or plate-like members, the ink aggregates on the partitions and plate-like members, or on the pixel electrodes. [Prior Art Document] [Patent Document]

[Patent Document 1] Japanese Patent Application No. 2000-187111 [Patent Document 2] Japanese Patent Application No. 2011-23305 [Patent Document 3] Japanese Patent Application No. 2018-527258

[The problem that the invention aims to solve]

The present invention was developed in light of the above circumstances. The problem to be solved is to provide a cured film for use in liquid crystal display devices, organic electroluminescent devices, and the like. The photosensitive resin composition of the present invention imparts high lyophilicity to the cured film, thereby suppressing uneven coating of an overlying material applied by inkjet or slit coating methods. [Means for Solving the Problem]

The present invention relates to the following: 1. A photosensitive resin composition suitable for use as a material for the first bank in a display device in which individual pixels are defined by providing first and second banks directly or through other layers on a substrate, the composition comprising the following components: (A) an alkali-soluble resin, (B) a fluorine-containing thermally decomposable polymer, (C) a solvent, and (D) a photosensitive agent. 2. The photosensitive resin composition according to item 1 above, wherein, on a substrate, the first bank is formed to be located adjacent to the second bank, and/or to be isolated within an area surrounded by the second bank, and/or to intersect with the second bank; and the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface. 3. The photosensitive resin composition according to item 1 above, wherein, on a substrate, the second bank is formed to be located directly above the first bank or via another layer; and the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface. 4. The photosensitive resin composition according to any one of items 1 to 3 above, wherein the fluorinated thermally decomposable polymer of component (B) comprises: a main chain (a) having a polymer structure of a polymerizable monomer and a side chain (b) having a functional group represented by the following general formula (1); (wherein ^R1 , ^R2 , and ^R3 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, ^R4 is a fluorinated alkyl group or a poly(perfluoroalkylene ether) chain; and ^Y1 is an oxygen atom or a sulfur atom.) 5. The photosensitive resin composition according to any one of 1 to 4 above, wherein ^R4 is a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom. 6. The photosensitive resin composition according to any one of 1 to 4 above, wherein ^R4 is a fluorinated alkyl group having 4 to 6 carbon atoms directly bonded to a fluorine atom. 7. The photosensitive resin composition according to any one of 1 to 4 above, wherein R ¹ , R ² , and R ³ are each independently a hydrogen atom, and R ⁴ is a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom. 8. The photosensitive resin composition according to any one of 1 to 4 above, wherein the side chain (b) represented by the general formula (1) is represented by the following formula (1-1); . 9. The photosensitive resin composition as described in any one of items 1 to 8 above, wherein the photosensitive resin composition satisfies at least any one of the following (Z1) to (Z4); (Z1): further contains a crosslinking agent as component (E), (Z2): the alkali-soluble resin further has a self-crosslinking group, or further has a group that reacts with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, (Z3): the photosensitive agent is a photoradical generator, and further contains a compound having two or more ethylenic double bonds as component (F), (Z4): The aforementioned photosensitive agent is a photoacid generator, and further contains a compound having two or more functional groups that form covalent bonds with the acid generated from the aforementioned photoacid generator as component (G). 10. The photosensitive resin composition described in any one of items 1 to 9 above, wherein the aforementioned photosensitive agent is a quinone diazide compound. 11. The photosensitive resin composition described in item 9 above, wherein the aforementioned photosensitive agent is a quinone diazide compound, and further satisfies either of the aforementioned (Z1) or (Z2). 12. The photosensitive resin composition described in item 11 above, wherein the aforementioned photosensitive agent is naphthoquinone diazide. 13. The photosensitive resin composition according to any one of items 1 to 12 above, wherein the number average molecular weight of the alkali-soluble resin is 2,000 to 50,000 in terms of polystyrene. 14. The photosensitive resin composition according to any one of items 1 to 13 above, wherein the fluorinated thermally decomposable polymer is contained in an amount of 0.01 to 1 part by mass per 100 parts by mass of the alkali-soluble resin. 15. The photosensitive resin composition according to any one of items 9 to 14 above, wherein the crosslinking agent is contained in an amount of 1 to 50 parts by mass per 100 parts by mass of the alkali-soluble resin. 16. The photosensitive resin composition according to any one of 1 to 15 above, wherein the display device comprises an organic thin film within the pixel area defined by the second bank and the first bank, and the organic thin film is used in a pixel of an organic electroluminescent device. 17. The photosensitive resin composition according to any one of 1 to 16 above, wherein the other layer is a hole injection layer of the organic electroluminescent device. 18. A cured film formed using the photosensitive resin composition according to any one of 1 to 17 above. 19. A display device comprising the cured film according to 18 above. 20. A method for manufacturing a display device having defined pixel areas, comprising: forming a first bank portion directly on a substrate or via another layer; and forming a second bank portion directly on the substrate or via another layer; wherein the first bank portion is formed from the photosensitive resin composition described in any one of items 1 to 17 above. [Effects of the Invention]

The photosensitive resin composition of the present invention exhibits high affinity for liquids. Cured films formed from this composition exhibit high affinity for liquids while improving wettability of overlying materials laminated using methods such as inkjet or slit coating, thereby suppressing uneven coating. Furthermore, display devices incorporating this cured film prevent ink from agglomerating on partition walls, plate-shaped components, or pixel electrodes during ink application, thus suppressing color mixing and enabling displays with high color purity.

[Form of implementing the invention]

The photosensitive resin composition of the present invention, a cured film formed from the photosensitive resin composition, and a method for manufacturing a display device having the cured film are described in detail below.

<Photosensitive Resin Composition> The following details the components of the photosensitive resin composition.

<Component (A)> Component (A) of the present invention is an alkali-soluble resin. To impart alkali solubility, the resin contains an alkali-soluble group. Examples of such groups include phenolic hydroxyl groups, carboxyl groups, acid anhydride groups, imide groups, sulfonyl groups, phosphoric acid groups, boric acid groups, active methylene groups, and active methine groups.

An active methylene group refers to a methylene group ( _-CH2- ) with a carbonyl group adjacent to it, which is reactive toward nucleophiles. Furthermore, the active methine group in the present invention refers to a group in which one of the hydrogen atoms of the methylene group is replaced by an alkyl group, which is reactive toward nucleophiles.

Among active methylene groups and active methine groups, active methylene groups are preferred, and active methylene groups represented by the following formula (a1) are more preferred. (In formula (a1), R represents an alkyl group, an alkoxy group, or a phenyl group, and the dotted line represents a bond).

In formula (a1), examples of the alkyl group represented by R include alkyl groups having 1 to 20 carbon atoms, preferably alkyl groups having 1 to 5 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, and isopropyl. Among them, methyl, ethyl, and n-propyl are preferred.

In formula (a1), examples of the alkoxy group represented by R include alkoxy groups having 1 to 20 carbon atoms, preferably alkoxy groups having 1 to 5 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, and tert-butoxy. Among them, methoxy, ethoxy, and n-propoxy are preferred.

Examples of the group represented by the above formula (a1) include the following structures. In the structural formula, a dotted line represents a bond.

Among the above-mentioned alkali-soluble groups, alkali-soluble resins having at least one organic group selected from the group consisting of phenolic hydroxyl groups and carboxyl groups and having a number average molecular weight of 2,000 to 50,000 are preferred.

The alkali-soluble resin of the component (A) is not particularly limited as long as it has the above-mentioned structure. The main chain skeleton and side chain types of the polymer constituting the resin are not particularly limited.

However, the number average molecular weight of the alkali-soluble resin of component (A) should be within the range of 2,000 to 50,000. If the number average molecular weight exceeds 50,000, development residue will be easily generated, significantly reducing sensitivity. On the other hand, if the number average molecular weight is less than 2,000, a considerable amount of film loss will occur in the exposed area during development, resulting in insufficient curing.

Examples of the alkali-soluble resin as component (A) include acrylic resins, polyhydroxystyrene resins, polyimide precursors, and polyimides.

Furthermore, in the present invention, an alkali-soluble resin composed of a copolymer obtained by polymerizing multiple monomers (hereinafter referred to as a specific copolymer) can also be used as component (A). In this case, the alkali-soluble resin of component (A) can be a blend of multiple specific copolymers.

Specifically, the specific copolymer described above comprises, as essential constituent units, an alkali-soluble monomer, namely, a monomer having at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group, and at least one selected from the group of monomers copolymerizable with the monomer, and has a number-average molecular weight of 2,000 to 50,000. A number-average molecular weight exceeding 50,000 may result in residue.

The aforementioned "monomer having at least one selected from the group consisting of a phenolic hydroxyl group and a carboxyl group" includes monomers having a phenolic hydroxyl group and monomers having a carboxyl group. These monomers are not limited to those having a single phenolic hydroxyl group or carboxyl group and may have multiple phenolic hydroxyl groups.

Specific examples of the above-mentioned monomers are listed below, but the present invention is not limited thereto. Examples of monomers having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, mono(2-(acryloyloxy)ethyl)phthalate, mono(2-(methacryloyloxy)ethyl)phthalate, N-(carboxyphenyl)maleimide, N-(carboxyphenyl)methacrylamide, and N-(carboxyphenyl)acrylamide.

Examples of the monomer having a phenolic hydroxyl group include hydroxystyrene, N-(hydroxyphenyl)acrylamide, N-(hydroxyphenyl)methacrylamide, N-(hydroxyphenyl)maleimide, and 4-hydroxyphenyl methacrylate.

The ratio of the unsaturated carboxylic acid derivative and/or monomer having a phenolic hydroxyl group to a polymerizable unsaturated group in the preparation of the alkali-soluble resin of component (A) is preferably 5 mol% to 90 mol%, more preferably 10 mol% to 60 mol%, and most preferably 10 mol% to 30 mol%, based on all monomers used in the preparation of the alkali-soluble resin of component (A). If the unsaturated carboxylic acid derivative content is less than 5% by weight, the alkali solubility of the polymer will be insufficient.

The alkali-soluble resin of component (A) of the present invention is preferably copolymerized with a monomer having a hydroxyalkyl group and a polymerizable unsaturated group from the viewpoint of further stabilizing the shape of the pattern after curing.

Examples of the monomer having a hydroxyalkyl group and a polymerizable unsaturated group include 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2,3-dihydroxypropyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2,3-dihydroxypropyl methacrylate, glycerol monomethacrylate, and 5-acryloyloxy-6-hydroxynorbornene-2-carboxy-6-lactone.

The ratio of monomers having hydroxyl alkyl groups and polymerizable unsaturated groups in the preparation of the alkali-soluble resin of component (A) is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. If the ratio of monomers having hydroxyl alkyl groups and polymerizable unsaturated groups is less than 5% by mass, the copolymer may not achieve a stable pattern shape. If the ratio is greater than 60% by mass, the alkali-soluble groups in component (A) may be insufficient, resulting in reduced properties such as developing properties.

The alkali-soluble resin of component (A) of the present invention is preferably one further copolymerized with an N-substituted maleimide compound from the viewpoint of increasing the glass transition temperature (hereinafter referred to as Tg) of the copolymer.

Examples of N-substituted maleimide compounds include N-methylmaleimide, N-ethylmaleimide, N-phenylmaleimide, and N-cyclohexylmaleimide. From the perspective of transparency, those without an aromatic ring are preferred. From the perspective of developing properties, transparency, and heat resistance, those with an aliphatic ring skeleton are more preferred, with cyclohexylmaleimide being the most preferred.

The ratio of N-substituted maleimide in the production of the alkali-soluble resin (component (A)) is preferably 5% to 60% by mass, more preferably 10% to 50% by mass, and most preferably 20% to 40% by mass. If the N-substituted maleimide content is less than 5% by mass, the Tg of the copolymer may be low, resulting in poor heat resistance. If it is greater than 60% by mass, transparency may be reduced.

When the photosensitive resin composition of the present invention satisfies requirement (Z2), the alkali-soluble resin of component (A) used in the present invention is preferably a copolymer further having a self-crosslinking group or a group reactive with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group (hereinafter also referred to as a crosslinking group).

Examples of the self-crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxacyclobutyl group, a vinyl group, and a blocked isocyanate group.

Examples of the crosslinking group include an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group.

When the alkali-soluble resin of component (A) contains the self-crosslinking group or crosslinking group, the content thereof is preferably 0.1 to 0.9 per repeating unit in the resin of component (A), and more preferably 0.1 to 0.8 from the viewpoint of developing properties and solvent resistance.

When the alkali-soluble resin of component (A) further has repeating units containing at least one type selected from a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxyheterobutyl group, a vinyl group, and a blocked isocyanate group, and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, and a blocked isocyanate group, for example, an unsaturated compound having free radical polymerizability and having a crosslinking group such as an epoxy group, an oxyheterobutyl group, a vinyl group, and a blocked isocyanate group, and a self-crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, and an alkoxysilyl group may be copolymerized.

Examples of the radically polymerizable unsaturated compound having an N-alkoxymethyl group include N-butoxymethylacrylamide, N-isobutoxymethylacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, and N-hydroxymethylacrylamide.

Examples of monomers having radical polymerizability and further having an N-hydroxymethyl group include N-hydroxymethacrylamide and N-hydroxymethylmethacrylamide.

Examples of monomers having radical polymerizability and further having an alkoxysilyl group include 3-acryloyloxytrimethoxysilane, 3-acryloyloxytriethoxysilane, 3-methacryloyloxytrimethoxysilane, and 3-methacryloyloxytriethoxysilane.

Examples of the unsaturated compound having free radical polymerizability and further having an epoxy group include glycidyl acrylate, glycidyl methacrylate, α-ethyl glycidyl acrylate, α-n-propyl glycidyl acrylate, α-n-butyl glycidyl acrylate, 3,4-epoxybutyl acrylate, 3,4-epoxybutyl methacrylate, 6,7-epoxyheptyl acrylate, 6,7-epoxyheptyl methacrylate, α-ethyl acrylate, 6,7-epoxyheptyl ether, 2-vinylbenzyl glycidyl ether, 3-vinylbenzyl glycidyl ether, 4-vinylbenzyl glycidyl ether, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate, 6,7-epoxyheptyl methacrylate, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, 3,4-epoxycyclohexyl methacrylate, etc. are preferably used. These can be used alone or in combination.

Examples of unsaturated compounds having free radical polymerizability and further having an oxycyclobutyl group include (meth)acrylates having an oxycyclobutyl group. Among these monomers, 3-(methacryloyloxymethyl)oxycyclobutane, 3-(acryloyloxymethyl)oxycyclobutane, 3-(methacryloyloxymethyl)-3-ethyl-oxycyclobutane, 3-(acryloyloxymethyl)-3-ethyl-oxycyclobutane, 3-(methacryloyloxymethyl)-2-trifluoromethyloxycyclobutane, 3-(acryloyloxymethyl)-2-trifluoromethyloxycyclobutane, 3-(methacryloyloxymethyl)-2-phenyl- cyclobutane, 3-(acryloyloxymethyl)-2-phenyl-cyclobutane, 2-(methacryloyloxymethyl)cyclobutane, 2-(acryloyloxymethyl)cyclobutane, 2-(methacryloyloxymethyl)cyclobutane, 2-(acryloyloxymethyl)cyclobutane, 2-(methacryloyloxymethyl)-4-trifluoromethylcyclobutane, 2-(acryloyloxymethyl)-4-trifluoromethylcyclobutane, preferably 3-(methacryloyloxymethyl)-3-ethylcyclobutane, 3-(acryloyloxymethyl)-3-ethylcyclobutane, etc.

Examples of monomers having radical polymerizability and further having a vinyl group include 2-(2-vinyloxyethoxy)ethyl acrylate and 2-(2-vinyloxyethoxy)ethyl methacrylate.

Examples of monomers having radical polymerizability and further having a blocked isocyanate group include 2-(0-(1'-methylpropyleneamino)carboxylamino)ethyl methacrylate and 2-(3,5-dimethylpyrazolyl)carbonylamino)ethyl methacrylate.

When the photosensitive resin composition of the present invention satisfies condition (Z2), it preferably contains 10% to 70% by mass, and particularly preferably 20% to 60% by mass, of constituent units derived from an unsaturated compound having free radical polymerizability and having a self-crosslinking group selected from N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, oxacyclobutyl, vinyl, and blocked isocyanate groups, and a crosslinking group selected from N-alkoxymethyl, N-hydroxymethyl, alkoxysilyl, epoxy, vinyl, and blocked isocyanate groups. If the content of this constituent unit is less than 10% by mass, the heat resistance and surface hardness of the resulting cured film tend to decrease. On the other hand, if the content of this constituent unit exceeds 70% by mass, the storage stability of the photosensitive resin composition tends to decrease.

Furthermore, in the present invention, the acrylic polymer of component (A) may be a copolymer formed from monomers other than the aforementioned monomers (hereinafter referred to as "other monomers") as constituent units. Specifically, the other monomers are not particularly limited, as long as they are copolymerizable with at least one monomer selected from the group consisting of the aforementioned monomers having a carboxyl group and monomers having a phenolic hydroxyl group, as long as they do not impair the properties of component (A). Specific examples of such monomers include acrylate compounds, methacrylate compounds, maleimide, acrylamide compounds, acrylonitrile, styrene compounds, and vinyl compounds. Specific examples of these other monomers are listed below, but are not intended to be limiting.

Examples of the acrylate compound include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthracene acrylate, anthracenyl methyl acrylate, phenyl acrylate, glycidyl acrylate, phenoxyethyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2-methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate, 8-methyl-8-tricyclodecyl acrylate, 8-ethyl-8-tricyclodecyl acrylate, diethylene glycol monoacrylate, 2-(acryloyloxy)ethyl caprolactone, and poly(ethylene glycol) ethyl ether acrylate.

Examples of the methacrylate compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthracene methacrylate, anthracenylmethyl methacrylate, phenyl methacrylate, glycidyl methacrylate, phenoxyethyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isoborneol methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, Ester, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2-methyl-2-adamantyl methacrylate, γ-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate, diethylene glycol monomethacrylate, 2-(methacryloyloxy)ethyl caprolactone, poly(ethylene glycol) ethyl ether methacrylate, etc.

Examples of the acrylamide compound include N-methylacrylamide, N-methylmethacrylamide, N,N-dimethylacrylamide, N,N-dimethylmethacrylamide, N-methoxymethylacrylamide, N-methoxymethylmethacrylamide, N-butoxymethylacrylamide, and N-butoxymethylmethacrylamide.

Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, cyclohexyl vinyl ether, vinyl naphthalene, vinyl anthracene, vinyl carbazole, allyl glycidyl ether, 3-vinyl-7-oxabicyclo[4.1.0]heptane, 1,2-epoxy-5-hexene, and 1,7-octadiene monocyclooxide.

Examples of the styrene compound include styrenes having no hydroxyl group, such as styrene, α-methylstyrene, chlorostyrene, and bromostyrene.

In the production of the alkali-soluble resin of component (A), the ratio of the aforementioned other monomers is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 20% by mass or less. If the ratio exceeds 80% by mass, the amount of the necessary components is relatively reduced, making it difficult to fully achieve the effects of the present invention.

The method for obtaining the alkali-soluble resin used as component (A) of the present invention is not particularly limited. For example, a monomer having at least one selected from the group consisting of a carboxyl group, a phenolic hydroxyl group, and a group that generates a carboxylic acid or a phenolic hydroxyl group by the action of heat or acid, a monomer having a hydroxyalkyl group, a monomer having an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, an oxadiazole group, an ethylene group, a hydroxyalkyl ... The present invention relates to a polyol obtained by polymerizing a monomer containing at least one group selected from a self-crosslinking group such as a blocked isocyanate group and a crosslinking group such as an N-alkoxymethyl group, an N-hydroxymethyl group, an alkoxysilyl group, an epoxy group, a vinyl group, or a blocked isocyanate group, in the presence of an optional other copolymerizable monomer and an optional polymerization initiator at a temperature of 50°C to 110°C. The solvent used is not particularly limited as long as it can dissolve the monomers constituting the alkali-soluble resin and the acrylic polymer having specific functional groups. Specific examples include the solvents described below for component (C).

The acrylic polymer having specific functional groups thus obtained is usually in the form of a solution dissolved in a solvent.

Furthermore, the solution of the specific copolymer obtained as described above is added to diethyl ether or water under stirring to allow it to reprecipitate. After filtering and washing the resulting precipitate, it is dried at room temperature or under heat under normal pressure or reduced pressure to obtain a powder of the specific copolymer. By such an operation, the polymerization initiator or unreacted monomer coexisting with the specific copolymer can be removed, resulting in a purified powder of the specific copolymer. If a single operation cannot fully purify the specific copolymer, the obtained powder can be redissolved in a solvent and the above operation can be repeated. In the present invention, the powder of the specific copolymer can be used directly, or the powder can be redissolved in, for example, component (C) described below and used as a solution.

Furthermore, as the alkali-soluble resin of component (A), polyimide precursors such as polyamic acid, polyamic acid esters, partially imidized polyamic acid, and polyimides such as carboxylic acid group-containing polyimides can be used. As long as they are alkali-soluble, their types are not limited.

The polyamide as the polyimide precursor can generally be obtained by polycondensing (i) a tetracarboxylic dianhydride compound and (j) a diamine compound.

The tetracarboxylic dianhydride compound (i) is not particularly limited. Specific examples thereof include aromatic tetracarboxylic acids such as pyromellitic dianhydride, 3,3,'4,4'-biphenyl tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ketone tetracarboxylic dianhydride, 3,3,'4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3,'4,4'-diphenylsulfonium tetracarboxylic dianhydride, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 1,2- Alicyclic tetracarboxylic dianhydrides such as dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2,3,4-cyclohexanetetracarboxylic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride; and aliphatic tetracarboxylic dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride. These compounds can be used alone or in combination of two or more.

Furthermore, the diamine compound (j) is not particularly limited. Examples thereof include 2,4-diaminobenzoic acid, 2,5-diaminobenzoic acid, 3,5-diaminobenzoic acid, 4,6-diamino-1,3-benzenedicarboxylic acid, 2,5-diamino-1,4-benzenedicarboxylic acid, bis(4-amino-3-carboxyphenyl)ether, bis(4-amino-3,5-dicarboxyphenyl)ether, bis(4-amino-3-carboxyphenyl)ether, Bis(4-amino-3,5-dicarboxyphenyl)sulfonium, 4,4'-diamino-3,3'-dicarboxybiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethylbiphenyl, 4,4'-diamino-3,3'-dicarboxy-5,5'-dimethoxybiphenyl, 1,4-bis(4-amino-3-carboxyphenoxy)benzene, 1,3-bis(4-amino-3-carboxyphenyl)sulfonium phenoxy)benzene, bis[4-(4-amino-3-carboxyphenoxy)phenyl]sulfone, bis[4-(4-amino-3-carboxyphenoxy)phenyl]propane, 2,2-bis[4-(4-amino-3-carboxyphenoxy)phenyl]hexafluoropropane, 2,4-diaminophenol, 3,5-diaminophenol, 2,5-diaminophenol, 4,6-diaminoresorcinol, 2,5-diaminohydroquinone, bis(3 -amino-4-hydroxyphenyl) ether, bis(4-amino-3-hydroxyphenyl) ether, bis(4-amino-3,5-dihydroxyphenyl) ether, bis(3-amino-4-hydroxyphenyl)methane, bis(4-amino-3-hydroxyphenyl)methane, bis(4-amino-3,5-dihydroxyphenyl)methane, bis(3-amino-4-hydroxyphenyl)sulfonium, bis(4-amino-3-hydroxyphenyl)sulfonium, bis(4-amino 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3-hydroxyphenyl)hexafluoropropane, 2,2-bis(4-amino-3,5-dihydroxyphenyl)hexafluoropropane, 4,4'-diamino-3,3'-dihydroxybiphenyl, 4,4'-diamino-3,3'-dihydroxy-5,5'-dimethylbiphenyl, 4,4 '-Diamino-3,3'-dihydroxy-5,5'-dimethoxybiphenyl, 1,4-bis(3-amino-4-hydroxyphenoxy)benzene, 1,3-bis(3-amino-4-hydroxyphenoxy)benzene, 1,4-bis(4-amino-3-hydroxyphenoxy)benzene, 1,3-bis(4-amino-3-hydroxyphenoxy)benzene, bis[4-(3-amino-4-hydroxyphenoxy)phenyl]sulfonium, bis[4-( Diamine compounds having a phenolic hydroxyl group such as 2,2-bis[4-(3-amino-4-hydroxyphenoxy)phenyl]hexafluoropropane, 1,3-diamino-4-alkylbenzene, 1,3-diamino-5-alkylbenzene, 1,4-diamino-2-alkylbenzene, bis(4-amino-3-alkylphenyl)ether, 2,2-bis(3-amino-4-alkylphenyl) Diamine compounds having a thiophenol group such as hexafluoropropane, and diamine compounds having a sulfonic acid group such as 1,3-diaminobenzene-4-sulfonic acid, 1,3-diaminobenzene-5-sulfonic acid, 1,4-diaminobenzene-2-sulfonic acid, bis(4-aminobenzene-3-sulfonic acid) ether, 4,4'-diaminobiphenyl-3,3'-disulfonic acid, and 4,4'-diamino-3,3'-dimethylbiphenyl-6,6'-disulfonic acid. In addition, p-phenylenediamine, m-phenylenediamine, 4,4'-methylene-bis(2,6-ethylaniline), 4,4'-methylene-bis(2-isopropyl-6-methylaniline), 4,4'-methylene-bis(2,6-diisopropylaniline), 2,4,6-trimethyl-1,3-phenylenediamine, 2,3,5,6-tetramethyl-1,4-phenylenediamine, o-toluidine, m-toluidine, 3,3,'5,5'-tetramethylbenzidine, bis[4-(3-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(3-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diamino-3,3 Diamine compounds such as '-dimethyldicyclohexylmethane, 4,4'-diaminodiphenyl ether, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane, 2,2-bis(4-anilino)hexafluoropropane, 2,2-bis(3-anilino)hexafluoropropane, 2,2-bis(3-amino-4-toluyl)hexafluoropropane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, bis[4-(4-aminophenoxy)phenyl]sulfone, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, and 2,2'-bis(trifluoromethyl)benzidine. These may be used alone or in combination of two or more compounds.

When the polyamide used in the present invention is produced from (i) a tetracarboxylic dianhydride compound and (j) a diamine compound, the blending ratio of the two compounds, i.e., the total molar number of the (j) diamine compound/the total molar number of the (i) tetracarboxylic dianhydride compound, is preferably 0.7 to 1.2. As in conventional polycondensation reactions, the closer this molar ratio is to 1, the greater the degree of polymerization and molecular weight of the resulting polyamide.

Furthermore, when using an excess of a diamine compound during polymerization, the remaining terminal amino groups of the polyamide can be protected by reacting with a carboxylic anhydride. Examples of such carboxylic anhydrides include phthalic anhydride, trimellitic anhydride, maleic anhydride, naphthalic anhydride, hydrophthalic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, itaconic anhydride, and tetrahydrophthalic anhydride.

In the production of polyamides, the reaction temperature of the diamine compound and the tetracarboxylic dianhydride compound can be selected from -20°C to 150°C, preferably from -5°C to 100°C. To obtain high-molecular-weight polyamides, the reaction temperature is preferably between 5°C and 40°C, and the reaction time is preferably between 1 and 48 hours. To obtain low-molecular-weight, highly stable, partially imidized polyamides, the reaction temperature is preferably between 40°C and 90°C, and the reaction time is preferably at least 10 hours. When protecting the terminal amino groups with anhydrides, the reaction temperature can be selected from -20°C to 150°C, preferably from -5°C to 100°C.

The reaction of the diamine compound and the tetracarboxylic dianhydride compound can be carried out in a solvent. Examples of the solvent that can be used include N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, N-vinylpyrrolidone, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfoxide, hexamethylsulfoxide, m-cresol, γ-butyrolactone, ethyl acetate, butyl acetate, ethyl lactate, methyl 3-methoxypropionate, methyl 2-methoxypropionate, ethyl 3-methoxypropionate, ethyl 2-methoxypropionate, ethyl 3-ethoxypropionate, and ethyl 2-ethoxypropionate. , ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, carbitol acetate, ethyl cellulose acetate, cyclohexanone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, etc. These can be used alone or in combination. Furthermore, even if it is a solvent that does not dissolve polyamine, it can be mixed with the above-mentioned solvent and used within the range that the polyamine generated by the polymerization reaction does not precipitate.

The resulting polyamine solution can be used directly in the preparation of photosensitive resin compositions. Alternatively, the polyamine can be isolated by precipitation in a weak solvent such as water, methanol, or ethanol, and recovered for reuse.

As component (A), any polyimide can be used. The polyimide used in the present invention is obtained by chemically or thermally imidizing a polyimide precursor such as the aforementioned polyamic acid by 50% or more.

The polyimide used in the photosensitive resin composition of the present invention preferably has a group selected from the group consisting of a carboxyl group and a phenolic hydroxyl group in order to impart alkaline solubility. Methods for introducing carboxyl groups or phenolic hydroxyl groups into the polyimide include: using a monomer having a carboxyl group or a phenolic hydroxyl group; blocking the amine termini with an acid anhydride having a carboxyl group or a phenolic hydroxyl group; or reducing the imidization rate to 99% or less during the imidization of a polyimide precursor such as polyamide.

Such polyimides are obtained by synthesizing a polyimide precursor such as the aforementioned polyamide, followed by chemical imidization or thermal imidization. Chemical imidization generally involves adding excess acetic anhydride and pyridine to a polyimide precursor solution and reacting at room temperature to 100°C. Thermal imidization generally involves dehydrating the polyimide precursor solution while superheating it at 180°C to 250°C.

Furthermore, as the alkali-soluble resin of component (A), a phenol novolac resin can be further used.

Alternatively, a polyester polycarboxylic acid can be used as the alkali-soluble resin of component (A). Polyester polycarboxylic acids can be obtained from an acid dianhydride and a diol by the method described in WO2009/051186. Examples of the acid dianhydride include the aforementioned (i) tetracarboxylic dianhydride. Examples of the diol include aromatic diols such as bisphenol A, bisphenol F, 4,4'-dihydroxybiphenyl, benzene-1,3-dimethanol, and benzene-1,4-dimethanol; alicyclic diols such as hydrogenated bisphenol A, hydrogenated bisphenol F, 1,4-cyclohexanediol, 1,3-cyclohexanedimethanol, and 1,4-cyclohexanedimethanol; and aliphatic diols such as ethylene glycol, propylene glycol, 1,4-butanediol, and 1,6-hexanediol.

In the present invention, the alkali-soluble resin of component (A) may be a mixture of multiple alkali-soluble resins.

<Component (B)> Component (B) of the present invention is a fluorinated thermally decomposable polymer. Fluorinated thermally decomposable polymers are characterized by being thermally decomposable and comprising: a main chain (a) having a polymer structure comprising a polymerizable monomer; and a side chain (b) having a functional group represented by the aforementioned general formula (1). Herein, "thermoly decomposable" refers to polymers that thermally decompose upon exposure to an environment of 50-300°C for 30 minutes. For example, in the case of a fluorinated thermally decomposable polymer having carboxyl groups as component (B), exposure to an environment of 50-300°C for 30 minutes dissociates the structure protecting the carboxyl groups, generating carboxyl groups. Examples of the fluorine-containing thermally decomposable polymer as component (B) include a polymer having a main chain having a polymer structure of a polymerizable monomer, side chains having fluorinated alkyl groups and/or poly(perfluoroalkylene ether) chains, and side chains having a group having a structure represented by the aforementioned general formula (1).

In the side chain (b) having the functional group represented by the general formula (1), R ¹ , R ² and R ³ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms. Furthermore, R ¹ , R ² and R ³ are each preferably a hydrogen atom. ^{Y 1} is an oxygen atom or a sulfur atom.

In the side chain (b) having the functional group represented by the general formula (1), ^R4 is a fluorinated alkyl group or a poly(perfluoroalkylene ether) chain. Furthermore, a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to the fluorine atom is preferred from the viewpoint of obtaining a fluorinated thermally decomposable polymer exhibiting excellent smoothness. A fluorinated alkyl group having 4 to 6 carbon atoms directly bonded to the fluorine atom is more preferred, and a fluorinated alkyl group having 6 carbon atoms directly bonded to the fluorine atom is particularly preferred.

The aforementioned R ⁴ represents, for example, any one of the following formulae (Rf-1) to (Rf-7).

In the above formulas (Rf-1) to (Rf-4), n is, for example, an integer of 1 to 6, preferably an integer of 4 to 6. In the above formula (Rf-5), m is, for example, an integer of 1 to 18, n is an integer of 0 to 5, and the total of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, n is an integer of 0 to 4, and the total of m and n is 4 to 5. In the above formula (Rf-6), m is, for example, an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, p is an integer of 0 to 5, and the total of m, p, and the product of n and l is 2 to 71. Preferably, m is an integer of 1 to 3, n is an integer of 1 to 3, l is an integer of 1 to 6, p is an integer of 0 to 2, and the total product of m, p, n and l is ² to 23. Formula (Rf-6) represents a poly(perfluoroalkylene ether) chain.

As specific examples of R ⁴ , for example, the following formulas (γ1-1) to (γ1-4) can be preferably exemplified.

In the formulas (γ1-1) to (γ1-3), n is, for example, 0 to 5. In the formula (γ1-4), n is, for example, 0 to 20.

Preferred examples of the side chain (b) include the following. Among these, the side chain represented by formula (1-1) is preferred because it can be obtained using industrially available raw materials and is easy to synthesize. It is a fluorinated thermally decomposable polymer that exhibits excellent smoothness due to its low surface free energy.

The fluorinated thermally decomposable polymer of the present invention may contain side chains (b') other than those represented by the aforementioned general formula (1) within the scope of not impairing the effects of the present invention. Examples of the side chains (b') include those represented by the following general formula (1').

(In the formula, R ¹¹ , R ²¹ , and R ³¹ are each a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴¹ is an organic group having 1 to 18 carbon atoms, R ³¹ and R ⁴¹ may bond to each other to form a heterocyclic ring with Y ¹¹ as a heteroatom, and Y ¹¹ is an oxygen atom or a sulfur atom).

In the side chain (b') having a functional group represented by the aforementioned general formula (1'), R ¹¹ , R ²¹ , and R ³¹ are each a hydrogen atom, R ⁴¹ is an organic group having 1 to 18 carbon atoms, and Y ¹ is an oxygen atom or a sulfur atom. Since the difference in polarity between the protected carboxyl group and the activated carboxyl group is large, a fluorine-containing thermally decomposable polymer is preferably obtained, which enables a cured coating such as a resist film or a color filter protective film to be obtained, which has both smoothness and recoatability. More preferably, the side chain is represented by the following formula (1'-1).

The fluorinated thermally decomposable polymer may be a commercially available one having a polymer structure of a polymerizable monomer as a main chain, a side chain having a fluorinated alkyl group and/or a poly(perfluoroalkylene ether) chain, and a side chain having a group having a structure represented by the general formula (1). For example, DS-21 (manufactured by DIC Corporation) can be cited.

In the present invention, the fluorine-containing thermally decomposable polymer is preferably contained in an amount of 0.01 to 10 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the alkali-soluble resin.

<Component (C)> Component (C) used in the present invention serves as a solvent to dissolve components (A), (B), and, if necessary, (D) and (E), as well as other additives, as described below. As long as the solvent has such solubility, its type and structure are not particularly limited.

Examples of the component (C) include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellulose acetate, ethyl cellulose acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, 2-methyl-3-pentanone, 2-methyl-4-pentanone, 2-methyl-5-pentanone, 2-methyl-6-pentanone, 2-methyl-7-pentanone, 2-methyl-8-pentanone, 2-methyl-9-pentanone, 2-methyl-10 ... Ester, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutyrate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N,N-dimethylformamide, N,N-dimethylacetamide and N-methylpyrrolidone, etc.

These solvents may be used alone or in combination of two or more. Among these components (C), solvents without a hydroxyl group are preferred from the viewpoint of not dissolving the underlying membrane, namely, methyl cellulose acetate, ethyl cellulose acetate, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl-2-pentanone, 2-pentanone, 2-heptanone, γ-butyrolactone, ethyl ethoxylate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents are commonly used as photoresist solvents. When using a solvent with a hydroxyl group, it is preferable to use it in combination with a solvent without a hydroxyl group, as mentioned above, to prevent dissolving the underlying film. The solvent combination can be a single type or two or more, and there is no particular limitation, as long as it provides good coating properties and does not dissolve the underlying film. In this case, to prevent dissolving the underlying film, the amount of the hydroxyl group-containing solvent relative to the total weight of component (C) is preferably 70% by weight or less, more preferably 60% by weight or less, even more preferably 50% by weight or less, and most preferably 30% by weight or less.

<Component (D)> Component (D) includes the photosensitive agent (D-1) a 1,2-quinonediazide compound, (D-2) a photoradical generator, and (D-3) a photoacid generator.

As the (D-1) 1,2-quinonediazide compound, a compound having either a hydroxyl group or an amino group, or having both a hydroxyl group and an amino group, preferably 10 mol% to 100 mol% of the hydroxyl group or amino group (in the case of a compound having both hydroxyl and amino groups, the total amount thereof), and particularly preferably 20 mol% to 95 mol% of a compound esterified or amidated with 1,2-quinonediazidesulfonic acid, can be used. Examples of the 1,2-quinonediazidesulfonic acid include 1,2-naphthoquinone-2-diazide-5-sulfonic acid, 1,2-naphthoquinone-2-diazide-4-sulfonic acid, and 1,2-benzoquinone-2-diazide-4-sulfonic acid. Chlorides of these 1,2-quinonediazidesulfonic acids can be used in the reaction with the aforementioned compounds having either or both hydroxyl or amino groups. As the 1,2-quinonediazide compound (D-1), naphthoquinone diazide can be used.

Examples of the compound having a hydroxyl group include phenol, o-cresol, m-cresol, p-cresol, hydroquinone, resorcinol, catechol, methyl gallate, ethyl gallate, 1,3,3-tris(4-hydroxyphenyl)butane, 4,4-isopropylidenediphenol, 2,2-bis(4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 4,4'-dihydroxyphenylsulfone, 4,4-hexafluoroisopropylidenediphenol, 4,4',4"-trishydroxyphenylethane, 1,1,1-trishydroxyphenylethane, 4,4'-[1-[4-[1-(4-hydroxyphenyl)-1-methyl Phenolic compounds such as [ethyl]phenyl]ethylene]bisphenol, 2,4-dihydroxydiphenyl ketone, 2,3,4-trihydroxydiphenyl ketone, 2,2,'4,4'-tetrahydroxydiphenyl ketone, 2,3,4,4'-tetrahydroxydiphenyl ketone, 2,2',3,4,4'-pentahydroxydiphenyl ketone, 2,5-bis(2-hydroxy-5-methylbenzyl)methyl, and aliphatic alcohols such as ethanol, 2-propanol, 4-butanol, cyclohexanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 2-methoxyethanol, 2-butoxyethanol, 2-methoxypropanol, 2-butoxypropanol, ethyl lactate, and butyl lactate.

Examples of the amino group-containing compound include aniline, o-toluidine, m-toluidine, p-toluidine, 4-aminodiphenylmethane, 4-aminodiphenyl, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminophenylmethane, 4,4'-diaminodiphenyl ether, and the like, and aminocyclohexane.

Furthermore, examples of compounds containing both hydroxyl and amino groups include 4-aminophenol, 5-aminophenol, 4-aminoresorcinol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, bis(4-amino-3-carboxylic acid)phenol, 2,3-diaminophenol, 2,4-diaminophenol, 4,4'-diamino-4"-hydroxytriphenylmethane, 4-amino-4',4"-dihydroxytriphenylmethane, 4-amino-3-carboxylic acid Aminophenols such as bis(4-amino-3-carboxy-5-hydroxyphenyl)ether, bis(4-amino-3-carboxy-5-hydroxyphenyl)methane, 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)propane, and 2,2-bis(4-amino-3-carboxy-5-hydroxyphenyl)hexafluoropropane; and alkanolamines such as 2-aminoethanol, 3-aminopropanol, and 4-aminocyclohexanol.

These 1,2-quinonediazide compounds can be used alone or in combination of two or more.

When the photosensitive resin composition of the present invention is a positive-working photosensitive resin composition, the content of the compound having a quinonediazide group as component (D-1) is preferably 5 to 100 parts by mass, more preferably 8 to 50 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). If the content is less than 5 parts by mass, the difference in dissolution rate between the exposed and unexposed areas of the positive-working photosensitive resin composition in the developer becomes small, making patterning by development difficult. If the content exceeds 100 parts by mass, the 1,2-quinonediazide compound may not be fully dissolved with short exposure times, resulting in reduced sensitivity, or component (D-1) may absorb light, reducing the transparency of the cured film.

(D-2) The photoradical generator is not particularly limited as long as it generates radicals upon exposure. Specific examples include the same (D-2) listed for component (D) used in the upper film-forming composition. Specific examples include phenyl ketone, Michler's ketone, 4,4'-bis(diethylamino)phenyl ketone, 4-methoxy-4'-dimethylaminophenyl ketone, aromatic ketones such as 2-ethylanthraquinone and phenanthrene, benzoin ethers such as benzoin methyl ether, benzoin ethyl ether, and benzoin phenyl ether, benzoins such as methyl benzoin and ethyl benzoin, 2-(o-chlorophenyl)-4,5-phenylimidazole dibenzoate, and the like. polymers, 2-(o-chlorophenyl)-4,5-di(m-methoxyphenyl)imidazole dimers, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimers, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimers, 2,4,5-triarylimidazole dimers, 2-(o-chlorophenyl)-4,5-di(m-methylphenyl)imidazole dimers, 2-benzyl-2-dimethylamino-1-(4 -oxo-phenyl)-butanone, 2-trichloromethyl-5-phenylvinyl-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-cyanophenylvinyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(p-methoxyphenylvinyl)-1,3,4-oxadiazole and other halogenated methyloxadiazole compounds, 2,4-bis(trichloromethyl)-6-p-methoxyphenylvinyl-S-triazole, 2,4 -bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-S-trioxan, 2-trichloromethyl-4-amino-6-p-methoxyphenyl-S-trioxan, 2-(naphthyl-1-yl)-4,6-bis-trichloromethyl-S-trioxan, 2-(4-ethoxy-naphthyl-1-yl)-4,6-bis-trichloromethyl-S-trioxan, 2-(4-butoxy-naphthyl)- Halogenated methyl-S-trioxanone compounds such as 4,6-bis-trichloromethyl-S-trioxanone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-[4-(methylthio)phenyl]-2-oxolinylpropane, 1,2-benzyl-2-dimethylamino-1-(4-oxolinylphenyl)-butanone-1,1-hydroxy-cyclohexyl-phenyl ketone, diphenylethylene ketone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-4'-methyldiphenyl sulfide, benzyl methyl ketal, dimethylaminobenzoate, isoamyl p-dimethylaminobenzoate, 2-n-butoxyethyl-4-dimethylaminobenzoate, 2-chlorothiazolone, 2,4-diethylthiazolone, 2,4-dimethylthioxanthone, isopropylthiazolone, 1-(4-phenylthiophenyl) )-1,2-octanedione-2-(O-benzoyl oxime), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyl oxime), 4-benzoyl-methyldiphenyl sulfide, 1-hydroxy-cyclohexyl-phenyl ketone, 2-benzyl-2-(dimethylamino)-1-[4-(4-oxolinyl)phenyl]-1-butanone, 2-(dimethylamino)-1-[4-(4-oxolinyl)phenyl]-1-butanone, methylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone, α-dimethoxy-α-phenylacetophenone, phenylbis(2,4,6-trimethylbenzyl)phosphine oxide, diphenyl(2,4,6-trimethylbenzyl)phosphine oxide, 2-methyl-1-[4-(methylthio)phenyl]-2-(4-morpholinyl)-1-propanone, etc. The above-mentioned photo-free radical generators are easily available as commercial products. Specific examples thereof include IRGACURE 173, IRGACURE 500, IRGACURE 2959, IRGACURE 754, IRGACURE 907, IRGACURE 369, IRGACURE 1300, IRGACURE 819, IRGACURE 819DW, IRGACURE 1880, IRGACURE 1870, DAROCURE TPO, DAROCURE 4265, IRGACURE 784, IRGACURE OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04, and IRGACURE 250 (all manufactured by BASF), KAYACURE DETX-S, KAYACURE CTX, and KAYACURE BMS, KAYACURE 2-EAQ (all manufactured by Nippon Kayaku Co., Ltd.), TAZ-101, TAZ-102, TAZ-103, TAZ-104, TAZ-106, TAZ-107, TAZ-108, TAZ-110, TAZ-113, TAZ-114, TAZ-118, TAZ-122, TAZ-123, TAZ-140, TAZ-204 (all manufactured by Midori Chemical Co., Ltd.), etc. These photo-free radical generators can be used individually or in combination.

When component (D-2) is included in the photosensitive resin composition of the present invention, its content is preferably 0.1 to 30 parts by mass, more preferably 0.5 to 20 parts by mass, and particularly preferably 1 to 15 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). If this ratio is too low, the exposed areas may not be sufficiently cured, making it impossible to form a pattern, or even if it is possible, the film may have low reliability. If this ratio is too high, the transmittance of the coating may decrease, or poor development may occur in the unexposed areas.

The photoacid generator (D-3) is not particularly limited as long as it is a compound that generates an acid by photodecomposition upon irradiation with ultraviolet light. Examples of the acid generated upon photodecomposition of the photoacid generator include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethanesulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, trimethylbenzenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H,1H,2H,2H-perfluorooctanesulfonic acid, perfluoro(2-ethoxyethane)sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzenesulfonic acid, and the like, or hydrates or salts thereof.

Examples of photoacid generators include diazomethane compounds, onium salt compounds, sulfonimide compounds, disulfonium compounds, sulfonic acid derivative compounds, nitrobenzyl compounds, benzoin toluenesulfonate compounds, iron aromatic hydrocarbon complexes, halogen-containing tris(onium) compounds, acetophenone derivative compounds, and cyano-containing oxime sulfonate compounds. Known or commonly used photoacid generators can be used in the present invention without particular limitation. In the present invention, the photoacid generator of component (D) can be used alone or in combination of two or more. Specific examples include compounds represented by the following formulas [PAG-1] to [PAG-41].

When component (D-3) is included in the photosensitive resin composition of this embodiment, the content is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 8 parts by mass, relative to 100 parts by mass of the total of components (A) and (B). By setting the content of component (D-3) to 0.01 parts by mass or greater, sufficient heat curing properties and solvent resistance can be imparted. However, if the content exceeds 20 parts by mass, unexposed areas may exhibit poor development, or the storage stability of the composition may be reduced.

<Component (E)> Component (E) is a crosslinking agent introduced into the photosensitive resin composition of the present invention when the composition satisfies requirement (Z1). More specifically, it is a compound having a structure capable of forming a crosslinked structure by thermally reacting with the thermally reactive sites (e.g., carboxyl groups and/or phenolic hydroxyl groups) of component (A). Specific examples are given below, but the invention is not limited thereto. Preferred thermal crosslinking agents include, for example, (E1) a crosslinking compound having two or more substituents selected from alkoxymethyl groups and hydroxymethyl groups, or (E2) a crosslinking compound selected from the crosslinking compounds represented by the following formula (2). These crosslinking agents may be used alone or in combination of two or more.

The crosslinkable compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups in component (E1) undergoes a crosslinking reaction by dehydration condensation when exposed to high temperatures during thermal curing. Examples of such compounds include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and phenolic plastic compounds.

Specific examples of alkoxymethylated glycoluril include 1,3,4,6-tetrakis(methoxymethyl)glycoluril, 1,3,4,6-tetrakis(butoxymethyl)glycoluril, 1,3,4,6-tetrakis(hydroxymethyl)glycoluril, 1,3-bis(hydroxymethyl)urea, 1,1,3,3-tetrakis(butoxymethyl)urea, 1,1,3,3-tetrakis(methoxymethyl)urea, 1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone, and 1,3-bis(methoxymethyl)-4,5-dimethoxy-2-imidazolidinone. Examples of commercially available products include glycoluril compounds (trade names: Cymel (registered trademark) 1170, Powder Link (registered trademark) 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name: UFR (registered trademark) 65), butylated urea resins (trade names: UFR (registered trademark) 300, U-VAN10S60, U-VAN10R, U-VAN11HV), and urea/formaldehyde-based resins (highly condensed type, trade names: Beckamine (registered trademark) J-300S, P-955, and N) manufactured by DIC Co., Ltd.

Specific examples of alkoxymethylated benzoguanamines include tetramethoxymethylbenzoguanamine. Commercially available products include those manufactured by Mitsui Cytec Co., Ltd. (trade name: Cymel (registered trademark) 1123) and Sanwa Chemical Co., Ltd. (trade names: Nikalac (registered trademark) BX-4000, BX-37, BL-60, and BX-55H).

Specific examples of alkoxymethylated melamine include hexamethoxymethylmelamine. Examples of commercially available products include methoxymethyl-type melamine compounds (trade names: Cymel (registered trademark) 300, 301, 303, and 350) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl-type melamine compounds (trade names: Mycoat (registered trademark) 506 and 508), methoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MW-30, MW-22, MW-11, MW-100LM, MS-001, MX-002, MX-730, MX-750, and MX-035) manufactured by Sanwa Chemical Co., Ltd., and butoxymethyl-type melamine compounds (trade names: Nikalac (registered trademark) MX-45, MX-410, and MX-302), etc.

Alternatively, compounds may be obtained by condensing melamine compounds, urea compounds, glycoluril compounds, and benzoguanamine compounds in which the hydrogen atom of an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, U.S. Patent No. 6,323,310 discloses a high molecular weight compound produced from melamine and benzoguanamine compounds. Commercially available products of the aforementioned melamine compound include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the aforementioned benzoguanamine compound include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of phenolic plastic compounds include 2,6-bis(hydroxymethyl)phenol, 2,6-bis(hydroxymethyl)cresol, 2,6-bis(hydroxymethyl)-4-methoxyphenol, 3,3',5,5'-tetrakis(hydroxymethyl)biphenyl-4,4'-diol, 3,3'-methylenebis(2-hydroxy-5-methylbenzyl alcohol), 4,4'-(1-methylethylidene)bis[2-methyl-6-hydroxymethylphenol], 4,4'-methylenebis[2-methyl-6-hydroxymethylphenol], 4,4'-(1-methylethylidene)bis[2,6-bis(hydroxymethyl)phenol], 4,4'-methylenebis[2,6-bis(hydroxymethyl)phenol] )phenol], 2,6-bis(methoxymethyl)phenol, 2,6-bis(methoxymethyl)cresol, 2,6-bis(methoxymethyl)-4-methoxyphenol, 3,3,’5,5’-tetrakis(methoxymethyl)biphenyl-4,4’-diol, 3,3’-methylenebis(2-methoxy-5-methylbenzyl alcohol), 4,4’-(1-methylethylidene)bis[2-methyl-6-methoxymethylphenol], 4,4’-methylenebis[2-methyl-6-methoxymethylphenol], 4,4’-(1-methylethylidene)bis[2,6-bis(methoxymethyl)phenol], 4,4’-methylenebis[2,6-bis(methoxymethyl)phenol], etc. Commercially available products are also available. Specific examples include 26DMPC, 46DMOC, DM-BIPC-F, DM-BIOC-F, TM-BIP-A, BISA-F, BI25X-DF, and BI25X-TPA (all manufactured by Asahi Organic Materials Industries, Ltd.).

Furthermore, as component (E1), a polymer produced using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, or N-butoxymethylmethacrylamide, may also be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

Furthermore, the photosensitive resin composition of the present invention may contain a crosslinking compound represented by the following formula (2) as component (E2). (In the formula, k is an integer from 2 to 10, m is an integer from 0 to 4, and R is a k-valent organic group)

The component (E2) is not particularly limited as long as it is a compound having a cycloalkene oxide structure represented by formula (2). Specific examples thereof include the following formulas E2-1 and E2-2, or commercially available products shown below.

Examples of commercially available products include Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, Celloxide 3000 (trade names of DAICEL Co., Ltd.), Denacol EX-252 (trade name of Nagase Chemtex Co., Ltd.), CY175, CY177, CY179 (trade names of Huntsman Corporation), Araldite CY-182, CY-192, CY-184 (trade names of Huntsman Corporation), Epiclon 200, 400 (trade names of DIC Co., Ltd.), Epikote 871, 872 (trade names of Mitsubishi Chemical Co., Ltd.), ED-5661, ED-5662 (trade names of Celanese Coating (trade name) etc. Moreover, these cross-linking compounds can be used alone or in combination of two or more types.

Among these, from the perspective of heat resistance, solvent resistance, resistance to long-term baking and other processing resistance and transparency, preferred are compounds represented by Formula E2-1 and Formula E2-2 having a cyclohexene oxide structure, Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000.

Furthermore, as component E, a compound other than those listed as component (E1) or component (E2) that can form a crosslinked structure by thermally reacting with the thermally reactive portion (e.g., carboxyl group and/or phenolic hydroxyl group) of component (A) can also be used. Specifically, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, Epoxy compounds such as 1,3,5,6-tetraepoxypropyl-2,4-hexanediol, N,N,N,'N'-tetraepoxypropyl-m-xylenediamine, 1,3-bis(N,N-diepoxypropylaminomethyl)cyclohexane, and N,N,N,'N,'-tetraepoxypropyl-4,4'-diaminodiphenylmethane; isocyanate compounds such as VESTANAT B1358/100 and VESTAGON BF 1540 (all isocyanurate-type modified polyisocyanates, manufactured by DEGUSSA Japan Co., Ltd.); Takenate (registered trademark) B-882N and Takenate B-7075 (all isocyanurate-type modified polyisocyanates, manufactured by Mitsui Chemicals Co., Ltd.).

Furthermore, as the component E, a polymer having two or more structures capable of forming a crosslinked structure by thermally reacting with the thermally reactive sites (thermoreactive carboxyl groups and/or phenolic hydroxyl groups) of the component (A) can be used. Specifically, for example, there can be cited polymers produced using compounds having an epoxy group such as glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, polymers produced using compounds having an alkoxysilyl group such as 3-methacryloyloxypropyltrimethoxysilane, compounds having an isocyanate group such as 2-isocyanatoethyl methacrylate (Karenz MOI [registered trademark], manufactured by Showa Denko Co., Ltd.), 2-isocyanatoethyl acrylate (Karenz AOI [registered trademark], manufactured by Showa Denko Co., Ltd.), or 2-(0-[1'-methylpropyleneamino]carboxylamino)ethyl methacrylate (Karenz Polymers produced from compounds with blocked isocyanate groups, such as MOI-BM [registered trademark], manufactured by Showa Denko Co., Ltd., and 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (Karenz MOI-BP [registered trademark], manufactured by Showa Denko Co., Ltd.). These compounds can be used alone or in combination to produce polymers, or they can be combined with other compounds to produce polymers.

When the component (A) has a group reactive with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group, a compound having two or more groups represented by hydroxyl groups, carboxyl groups, amide groups, and amino groups may be used as the component (E).

These crosslinking compounds can be used alone or in combination of two or more.

When the crosslinking agent (E) is selected as the crosslinking agent in the photosensitive resin composition of the present invention, its content is 1 to 50 parts by mass, preferably 1 to 40 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of component (A). If the content of the crosslinking compound is too low, the density of crosslinks formed by the crosslinking compound is insufficient, and thus the effect of improving the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation may not be achieved. On the other hand, if the content exceeds 50 parts by mass, uncrosslinked crosslinking compound remains, and the heat resistance, solvent resistance, and resistance to long-term baking after pattern formation may be reduced, or the storage stability of the photosensitive resin composition may be deteriorated.

<Component (F)> Component (F) is a compound having two or more ethylenically polymerizable groups. A compound having two or more ethylenically polymerizable groups herein means a compound having two or more polymerizable groups in one molecule, with the polymerizable groups located at the molecular terminals. Such polymerizable groups are at least one type of polymerizable group selected from the group consisting of acrylate, methacrylate, vinyl, and allyl groups. This compound having two or more ethylenically polymerizable groups in component (F) preferably has a molecular weight (weight average molecular weight, when the compound is a polymer) of 1,000 or less, from the perspective of good compatibility with the components of the negative photosensitive resin composition of the present invention and not affecting developing properties.

Specific examples of such compounds include dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, tetrahydroxymethylpropane tetraacrylate, tetrahydroxymethylpropane tetramethacrylate, tetrahydroxymethylmethane tetraacrylate, and tetrahydroxymethylpropane tetraacrylate. Acrylates, tetrahydroxymethylmethane tetramethacrylate, trihydroxymethylpropane triacrylate, trihydroxymethylpropane trimethacrylate, 1,3,5-triacryloyl hexahydro-S-triacontium, 1,3,5-trimethylacryloyl hexahydro-S-triacontium, tris(hydroxyethylacryloyl)isocyanurate, tris(hydroxyethylmethacryloyl)isocyanurate, triacryloyl formal, trimethylacryloyl formal, 1,6-hexanediol acrylate, 1,6-hexanediol methyl Acrylates, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, 2-hydroxypropanediol diacrylate, 2-hydroxypropanediol dimethacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, isopropylene glycol diacrylate, isopropylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, N,N'-bis(acryloyl)cysteine, N , N’-bis(methacryloyl)cysteine, thiodiglycol diacrylate, thiodiglycol dimethacrylate, bisphenol A diacrylate, bisphenol A dimethacrylate, bisphenol F diacrylate, bisphenol F dimethacrylate, bisphenol S diacrylate, bisphenol S dimethacrylate, bisphenoxyethanol fluorene diacrylate, bisphenoxyethanol fluorene dimethacrylate, diallyl ether bisphenol A, o-diallyl bisphenol A, diallyl maleate, triallyl trimellitate, etc.

The above-mentioned multifunctional acrylate compound is easily available as a commercial product. Specific examples thereof include KYARAD T-1420, same as DPHA, same as DPHA-2C, same as D-310, same as D-330, same as DPCA-20, same as DPCA-30, same as DPCA-60, same as DPCA-120, same as DN-0075, same as DN-2475, same as R-526, same as NPGDA, same as PEG400DA, same as MANDA, same as R-167, same as HX-220, same as HX620, same as R-551, same as R-712, same as R-604, same as R-684, same as GPO-303, same as TMPTA, same as THE-330, same as TPA-320, same as TPA-330, same as PET-30, same as RP-1040 (all manufactured by Nippon Kayaku Co., Ltd.), Aronix M-210, same as M-240, same as M-6200, same as M-309, same as M-400, same as M-402, same as M-405, same as M-450, same as M-7100, same as M-8030, same as M-8060, same as M-1310, same as M-1600, same as M-1960, same as M-8100, same as M-8530, same as M-8560, same as M-9050 (all manufactured by Toa Goesei Co., Ltd.), Biscoat 295, same as 300, same as 360, same as GPT, same as 3PA, same as 400, same as 260, same as 312, same as 335HP (all manufactured by Osaka Organic Chemical Industry Co., Ltd.), A-9300, A-GLY-9E, A-GLY-20E, A-TMM-3, A-TMM-3L, A-TMM-3LM-N, A-TMPT, AD-TMP, ATM-35E, A-T MMT, A-9550, A-DPH, TMPT, 9PG, 701, 1206PE, NPG, NOD-N, HD-N, DOD-N, DCP, BPE-1300N, BPE-900, BPE-200, BPE-100, BPE-80N, 23G, 14G, 9G, 4G, 3G, 2G, 1G (all manufactured by Shin-Nakamura Chemical Industry Co., Ltd.). These compounds having two or more ethylenically polymerizable groups may be used alone or in combination.

When component (F) is included in the photosensitive resin composition of the present invention, its content is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass, and particularly preferably 50 to 150 parts by mass, relative to 100 parts by mass of component (A). If this ratio is too low, the exposed areas may not be sufficiently cured, making it impossible to form a pattern, or even if they can be formed, the film may have low reliability. If this ratio is too high, the coating may stick after prebaking, or unexposed areas may not dissolve properly during development.

<Component (G)> Component (G) used in the photosensitive resin composition of the present invention is a compound having two or more functional groups capable of forming covalent bonds with an acid. Examples of such functional groups capable of forming covalent bonds with an acid include epoxy groups, alkoxymethyl groups, and hydroxymethyl groups.

Examples of the compound having two or more epoxy groups include tris(2,3-epoxypropyl)isocyanurate, 1,4-butanediol diepoxypropyl ether, 1,2-epoxy-4-(epoxyethyl)cyclohexane, glycerol triepoxypropyl ether, diethylene glycol diepoxypropyl ether, 2,6-diepoxypropylphenyl epoxypropyl ether, 1,1,3-tris[epoxypropyl] ...1,2-epoxy-4-(epoxyethyl)cyclohexane, 1,2-epoxy- (2,3-Epoxypropoxy)phenyl]propane, 1,2-epoxyhexanedicarboxylic acid diepoxypropyl ester, 4,4'-methylenebis(N,N-diepoxypropylaniline), 3,4-epoxyepoxyhexylmethyl-3,4-epoxyepoxyhexanecarboxylate, trihydroxymethylethane triepoxypropyl ether, bisphenol-A-diepoxypropyl ether, and pentaerythritol polyepoxypropyl ether, etc.

Furthermore, as the compound having two or more epoxy groups, a commercially available compound can also be used from the viewpoint of easy availability. Specific examples (trade names) are listed below, but the present invention is not limited thereto: Epoxy resins having amino groups such as YH-434 and YH434L (manufactured by New Sun Chemical EPOXY Manufacturing Co., Ltd.); Epoxy resins having an oxadiene oxide structure such as Epolead GT-401, GT-403, GT-301, GT-302, Celloxide 2021, and Celloxide 3000 (manufactured by DAICEL Co., Ltd.); Bisphenol A epoxy resins such as Epikote 1001, 1002, 1003, 1004, 1007, 1009, 1010, and 828 (manufactured by Oil Shell EPOXY Co., Ltd. (now Mitsubishi Chemical Co., Ltd.)); Epikote 807 (manufactured by Oil Shell EPOXY Co., Ltd.); Bisphenol F-type epoxy resins such as those manufactured by EPOXY Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.); phenol novolac-type epoxy resins such as Epikote 152 and 154 (manufactured by Yuka Shell EPOXY Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.), EPPN201 and 202 (manufactured by Nippon Kayaku Co., Ltd.); cresol novolac-type epoxy resins such as EOCN-102, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (manufactured by Nippon Kayaku Co., Ltd.), and Epikote 180S75 (manufactured by Yuka Shell EPOXY Co., Ltd. (currently manufactured by Mitsubishi Chemical Co., Ltd.); Denacol EX-252 (manufactured by Nagase Chemtex Co., Ltd.), CY175, CY177, CY179, Araldite CY-182, CY-192, and CY-184 (all manufactured by Huntsman Corporation), Epiclon 200 and 400 (all manufactured by Dainippon Ink & Chemicals Co., Ltd. (now DIC Co., Ltd.)), Epikote 871 and 872 (all manufactured by Yuka Shell EPOXY Co., Ltd. (now Mitsubishi Chemical Co., Ltd.)), ED-5661 and ED-5662 (all manufactured by Celanese Coating Co., Ltd.); Denacol Aliphatic polyoxypropylene ethers such as EX-611, EX-612, EX-614, EX-622, EX-411, EX-512, EX-522, EX-421, EX-313, EX-314, and EX-321 (manufactured by Nagase Chemtex Co., Ltd.).

Alternatively, as a compound having two or more epoxy groups, a polymer having epoxy groups can be used. These polymers having epoxy groups can be produced, for example, by addition polymerization using an addition-polymerizable monomer having epoxy groups. Examples include addition polymers such as polyglycidyl acrylate, copolymers of glycidyl methacrylate and ethyl methacrylate, and copolymers of glycidyl methacrylate, styrene, and 2-hydroxyethyl methacrylate, as well as condensation polymers such as epoxy novolac.

Alternatively, the polymer having an epoxy group can also be produced by reacting a high molecular compound having a hydroxy group with a compound having an epoxy group such as epichlorohydrin or glycidyl tosylate.

The weight average molecular weight of such a polymer is, for example, 300 to 20,000.

These compounds having two or more epoxy groups can be used alone or in combination of two or more.

Examples of compounds having two or more substituents selected from alkoxymethyl and hydroxymethyl groups include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, alkoxymethylated melamine, and phenolic plastic compounds.

Specific examples of alkoxymethylated glycoluril are described in the above paragraph [0100].

Specific examples of alkoxymethylated benzoguanamine are described in the above paragraph [0101].

Specific examples of alkoxymethylated melamine are described in the above paragraph [0102].

Alternatively, compounds may be obtained by condensing melamine compounds, urea compounds, glycoluril compounds, and benzoguanamine compounds in which the hydrogen atom of an amino group is substituted with a hydroxymethyl group or an alkoxymethyl group. For example, U.S. Patent No. 6,323,310 discloses a high molecular weight compound produced from a melamine compound and a benzoguanamine compound. Commercially available products of the aforementioned melamine compound include Cymel (registered trademark) 303 (manufactured by Mitsui Cytec Co., Ltd.), and commercially available products of the aforementioned benzoguanamine compound include Cymel (registered trademark) 1123 (manufactured by Mitsui Cytec Co., Ltd.).

Specific examples of phenolic plastic compounds are described in the above paragraph [0104].

Furthermore, as the component (G), a polymer produced using an acrylamide compound or a methacrylamide compound substituted with a hydroxymethyl group or an alkoxymethyl group, such as N-hydroxymethacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethacrylamide, or N-butoxymethylmethacrylamide, may be used.

Examples of such polymers include poly(N-butoxymethylacrylamide), copolymers of N-butoxymethylacrylamide and styrene, copolymers of N-hydroxymethylmethacrylamide and methyl methacrylate, copolymers of N-ethoxymethylmethacrylamide and benzyl methacrylate, and copolymers of N-butoxymethylacrylamide, benzyl methacrylate, and 2-hydroxypropyl methacrylate. The weight-average molecular weight of such polymers is 1,000 to 50,000, preferably 1,500 to 20,000, and more preferably 2,000 to 10,000.

When the photosensitive resin composition of the present invention contains the compound having two or more functional groups forming covalent bonds via an acid (component (G)), the content thereof is preferably 5 to 200 parts by mass, and more preferably 50 to 150 parts by mass, based on 100 parts by mass of component (A). If this ratio is too low, the photocurability of the negative photosensitive resin composition may be reduced. On the other hand, if it is too high, the developability of the unexposed area may be reduced, which may cause residual film or residue.

<Component (H)> Component (H) is an adhesion promoter. The photosensitive resin composition of this invention is intended to improve adhesion to the substrate after development, and an adhesion promoter may be added. Specific examples of such adhesion promoters include chlorosilanes such as trimethylchlorosilane, dimethylvinylchlorosilane, methyldiphenylchlorosilane, and chloromethyldimethylchlorosilane, trimethylmethoxysilane, dimethyldiethoxysilane, methyldimethoxysilane, dimethylvinylethoxysilane, diphenyldimethoxysilane, phenyltriethoxysilane, vinyltrichlorosilane, γ-aminopropyltriethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ- Alkoxysilanes such as (N-piperidyl)propyltriethoxysilane, 3-ureidopropyltriethoxysilane, and 3-ureidopropyltrimethoxysilane; silazanes such as hexamethyldisilazane, N,N'-bis(trimethylsilyl)urea, dimethyltrimethylsilylamine, and trimethylsilimidazole; heterocyclic compounds such as benzotriazole, benzimidazole, indazole, imidazole, 2-benzylbenzimidazole, 2-benzylbenzothiazole, 2-benzylbenzothiazole, ureaazole, thiouracil, benzylimidazole, and benzylopyrimidine; or urea or thiourea compounds such as 1,1-dimethylurea and 1,3-dimethylurea.

Commercially available compounds such as those manufactured by Shin-Etsu Chemical Co., Ltd., Momentive Performance Materials Worldwide Inc., or Toray-Dow Corning Polysilicone Co., Ltd. can also be used as adhesion promoters. These commercial products are readily available. Component (H) may be one or a combination of two or more of the aforementioned adhesion promoters.

Among these (H) components, alkoxysilanes (i.e., silane coupling agents) are preferred in terms of obtaining good adhesion.

The amount of these adhesion promoters added is generally 0.1 to 20 parts by mass, preferably 0.5 to 10 parts by mass, per 100 parts by mass of component (A). Using more than 20 parts by mass may result in reduced sensitivity, while using less than 0.1 parts by mass may not provide the full effect of the adhesion promoter.

<Other Additives> Furthermore, the photosensitive resin composition used in the present invention may contain, as necessary, leveling agents, rheology modifiers, pigments, dyes, storage stabilizers, defoaming agents, surfactants, or dissolution enhancers such as polyphenols and polycarboxylic acids, as long as they do not impair the effectiveness of the present invention.

<Photosensitive Resin Composition> The photosensitive resin composition used in the present invention comprises the following components: (A), (B), (C), and (D), and may optionally further comprise one or more of: (E) a crosslinking agent; (F) a compound having two or more ethylenically polymerizable groups; (G) a compound having two or more functional groups capable of forming covalent bonds with an acid; (H) an adhesion promoter; and other additives. (A) Component: Alkali-soluble resin (B) Component: Fluorine-containing thermally decomposable polymer (C) Component: Solvent (D) Component: Photosensitizer

Preferred examples of the photosensitive resin composition used in the present invention are as follows. [1]: A photosensitive resin composition containing 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A), wherein these components are dissolved in component (C). [2]: A photosensitive resin composition containing 0.01 to 20 parts by mass of component (B) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (A), wherein these components are dissolved in component (C), and further wherein the component (D) is component (D-1). [3]: A photosensitive resin composition containing 0.01 to 20 parts by mass of component (B) and 5 to 100 parts by mass of component (D) per 100 parts by mass of component (A), wherein these components are dissolved in component (C), and a photosensitive resin composition containing 1 to 50 parts by mass of a crosslinking agent of component (E) per 100 parts by mass of the total of components (A) and (B), wherein the component (D) is a photosensitive resin composition of component (D-1). [4]: The photosensitive resin composition comprising 0.01 to 20 parts by mass of component (B) per 100 parts by mass of component (A), 5 to 200 parts by mass of component (F) per 100 parts by mass of the total of components (A) and (B), and 0.1 to 30 parts by mass of component (D) per 100 parts by mass of the total of components (A), (B) and (F). The component (D) is a photosensitive resin composition of component (D-2).

The solid content of the photosensitive resin composition used in the present invention is not particularly limited, as long as all components are uniformly dissolved in the solvent. Examples include 1% to 80% by mass, 5% to 60% by mass, or 10% to 50% by mass. The solid content herein refers to the total content of the photosensitive resin composition excluding component (C).

The method for preparing the photosensitive resin composition used in the present invention is not particularly limited. However, examples of the preparation method include dissolving component (B) in component (C), and then mixing in a predetermined ratio the alkali-soluble resin (component (A), the photosensitizer (component (D), optionally the crosslinking agent (component (E), the compound having two or more ethylenically polymerizable groups (component (F), the compound having two or more functional groups capable of forming covalent bonds via an acid (component (G), and the adhesion promoter (component (H))) to form a uniform solution. Alternatively, other additives may be added as needed during the appropriate stage of this preparation method to further mix the components.

When preparing the photosensitive resin composition of the present invention, the copolymer solution obtained by the polymerization reaction of component (C) can be used directly. In this case, components (A), (D), and, if necessary, (E), (F), (G), and (H) are added to the solution of component (B) to prepare the photosensitive resin composition. When a uniform solution is obtained, component (C) may be added for the purpose of adjusting the concentration. In this case, the component (C) used in the formation of the specific copolymer and the component (C) used to adjust the concentration in the preparation of the photosensitive resin composition may be the same or different.

The prepared photosensitive resin composition solution is preferably filtered using a filter with a pore size of about 0.2 μm before use.

<Cured Film Formed by Photosensitive Resin Composition> The photosensitive resin composition of the present invention is applied to a suitable substrate (e.g., a silicon/silicon dioxide coated substrate, a silicon nitride substrate, a metal (e.g., a substrate coated with aluminum, molybdenum, chromium, etc.), a glass substrate) by spin coating, flow coating, roll coating, slot coating, slot coating followed by spin coating, or inkjet coating. A coating can be formed by applying a coating to a substrate such as a quartz substrate, an ITO (indium tin oxide, hereinafter referred to as ITO) substrate, or a film (e.g., a triacetyl cellulose film, a cycloolefin polymer film, a cycloolefin copolymer film, a polyethylene terephthalate film, a polyester film, an acrylic film, a polyimide resin film), and then pre-drying it on a hot plate or in an oven. This coating is then heated to form a photosensitive resin film, which serves as an underlayer film, a resist film, etc.

The heat treatment conditions include, for example, a temperature of 70°C to 160°C and a heating time of 0.3 to 60 minutes. Preferably, the temperature and heating time are 80°C to 140°C and 0.5 to 10 minutes.

The thickness of the photosensitive resin film formed from the photosensitive resin composition is, for example, 0.1 μm to 30 μm, or 0.2 μm to 10 μm, or more preferably 0.3 μm to 8 μm.

A mask with a designated pattern is placed on the resulting coating, and the film is exposed to light such as ultraviolet light. Development is performed with an alkaline developer, and either the exposed or unexposed areas are washed out, depending on the material composition. The remaining patterned film is heated as needed at 80°C to 140°C for 0.5 to 10 minutes to obtain a sharp relief pattern.

Examples of usable alkaline developers include aqueous solutions of alkaline metal hydroxides such as potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide; aqueous solutions of quaternary ammonium hydroxides such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, and choline; and aqueous solutions of amines such as ethanolamine, propylamine, and ethylenediamine. Surfactants and the like may also be added to these developers.

Among the above, a 0.1-2.58 mass % aqueous solution of tetraethylammonium hydroxide is generally used as a photoresist developer. In the photosensitive resin composition of the present invention, this alkaline developer is also used to achieve good development without causing problems such as film swelling.

As a developing method, any method such as a coating method, a dipping method, or a rocking dipping method can be used. The developing time is usually 15 to 180 seconds.

After development, the photosensitive resin film is washed with running water for, for example, 20 to 120 seconds, and then air-dried using compressed air or compressed nitrogen or by rotation to remove moisture from the substrate, thereby obtaining a patterned film.

The patterned film is then post-baked for thermal curing. Specifically, by heating it using a hot plate or oven, a film with a good relief pattern and excellent heat resistance, transparency, flattening properties, low water absorption, and chemical resistance is obtained.

Post-baking is generally carried out at a temperature selected from the range of 140°C to 270°C, for 5 to 30 minutes on a hot plate or 30 to 90 minutes in an oven.

Then, by post-baking, a desired cured film having a good pattern shape can be obtained.

As described above, by patterning the cured film, a bank pattern can be formed in which residues of components of the resist material are unlikely to remain in areas outside the bank, and a uniform organic thin film can be formed in the areas divided by the bank.

<Double Bank Formation Step> The double bank portion in the present invention refers to the first bank portion and the second bank portion. During the double bank formation step, the arrangement pattern of the first and second banks is not particularly limited, as long as the second bank portion can function as a barrier, enhancing the wettability of the laminated overlying material and suppressing coating unevenness. Similarly, the contact angle between the banks is not limited, as long as the first bank portion's improved wettability and the second bank's barrier function are both achieved. Specifically, the contact angle of the first bank portion can be greater than, less than, or equal to the contact angle of the second bank portion. From the perspective of suppressing uneven coating of the laminated upper layer material, the contact angle of the first bank is preferably smaller than the contact angle of the second bank.

Several examples of double bank formation patterns are provided. For example, on a substrate or other layer, a first bank is formed so as to be adjacent to a second bank and/or to exist in isolation within the area surrounded by the second bank. Figure 4(a) is a schematic cross-sectional view taken along line B-B' in Figure 3. As shown in Figure 4(a), first banks 13 and 14 are formed adjacent to second banks 23 and 24. Also, on a substrate, a first bank is formed so as to intersect with a second bank, and a second bank is formed directly above the first bank or across another layer. For example, as shown in Figures 1 and 2, a first bank 11 is formed so as to intersect with second banks 21 and 22. Figure 2 is a cross-sectional view taken along the line A-A' of structure 100 in Figure 1 . As shown in Figure 2 , second banks 21 and 22 are formed on top of first bank 11. That is, second banks 21 and 22 are formed after first bank 11 is formed. Similarly, Figure 4(b) is a schematic cross-sectional view taken along the line C-C' of Figure 3 . As shown in Figure 4(b), second banks 23 and 24 are formed on top of first bank 12.

Furthermore, the first bank can be formed into a variety of patterns. Figure 5 is a plan view showing the arrangement of the first and second banks as an example. 15A, 16A, and 16A' denote openings, and 15B and 16B denote the first bank.

In any of the above-mentioned double bank forming steps, the height of the first bank from the substrate surface is always lower than the height of the second bank from the substrate surface.

The diagrams here only depict a cured film (bank) formed directly on a substrate using the photosensitive resin composition of the present invention, but this is ultimately an example. Other layers that can be formed on the aforementioned substrate include, for example, an organic electroluminescent device, a QD-OLED display, or a micro-LED display. For example, in the case of an organic electroluminescent device, examples include an anode, a cathode, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer, and a light-emitting layer. In the bank formation step of the present invention, when used in an organic electroluminescent device, the hole injection layer of the organic electroluminescent device is particularly suitable as the other layer. The other layer is composed of at least one layer. [Example]

The present invention is described below in more detail with reference to the following embodiments, but the present invention is not limited to these embodiments.

[Abbreviations Used in Examples] The abbreviations used in the following examples have the following meanings. MAA: Methacrylic acid MMA: Methyl methacrylate HEMA: 2-Hydroxyethyl methacrylate CHMI: N-cyclohexylmaleimide AIBN: Azobisisobutyronitrile PFHMA: 2-(perfluorohexyl)ethyl methacrylate KBM-503: 3-Methacryloxypropyltriethoxysilane PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate QD: α,α,α'-tris(4-hydroxyphenyl)-1- ... A compound synthesized by the condensation reaction of 1 mol of 4-ethyl-isopropylbenzene and 1.5 mol of 1,2-naphthoquinone-2-diazolidine-5-sulfonyl chloride. GT-401: Butanetetracarboxylic acid tetrakis(3,4-epoxycyclohexylmethyl)-modified ε-caprolactone CEL-2021P: 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate MPTS: γ-Methacryloxypropyltrimethoxysilane R-30: Megafac R-30 (trade name) manufactured by DIC Co., Ltd. R-40: Megafac R-40 (trade name) manufactured by DIC Co., Ltd.

[Determination of Number-Average Molecular Weight and Weight-Average Molecular Weight] The number-average molecular weight and weight-average molecular weight of the specific copolymers and specific crosslinkers obtained according to the following synthesis examples were determined using a GPC apparatus manufactured by JASCO Corporation (Shodex (registered trademark) columns KF803L and KF804L). Tetrahydrofuran (eluting solvent) was flowed through the column at a flow rate of 1 ml/min (column temperature 40°C). The number-average molecular weight (hereinafter referred to as Mn) and weight-average molecular weight (hereinafter referred to as Mw) are expressed in terms of polystyrene.

<Synthesis Example 1> 5.0g of MAA, 11.7g of CHMI, 8.3g of HEMA, 8.3g of MMA, and 1.7g of AIBN were dissolved in 52.5g of PGMEA and reacted at a temperature of 60°C to 100°C to obtain an acrylic polymer solution (solids concentration 40% by mass) (P1). The resulting acrylic polymer had an Mn of 4,100 and an Mw of 7,600.

<Synthesis Example 2> 5.0 g of PFHMA, 3.8 g of KBM-503, 1.5 g of HEMA, and 0.5 g of AIBN were dissolved in 25.32 g of PGME and reacted at 80°C for 20 hours to obtain an acrylic polymer solution (solids concentration 30% by mass) (P2). The resulting acrylic polymer had an Mn of 4800 and an Mw of 6700.

<Synthesis of Fluorinated Thermally Decomposable Polymer (Compound 1)> A fluorinated thermally decomposable polymer (Compound 1) was synthesized by the well-known method described in International Publication No. 2016/063719. The resulting Compound 1 had a molecular weight of Mn 2,500 and Mw 26,000.

<Example 1, Example 2, Comparative Example 1, Comparative Example 2, Comparative Example 3, Comparative Example 4, and Top Coating Materials> Positive-working photosensitive resin compositions for each Example, Comparative Example, and top coating material were prepared according to the compositions shown in Table 1 below. In the Examples, components (B), (C), (D), and (E) were mixed in the specified proportions with a solution of component (A). In the Comparative Examples and top coating materials, components (C), (D), and (E), optionally with component (H), a surfactant, and a repellent component, were mixed in the specified proportions with a solution of component (A). The mixture was stirred at room temperature for 3 hours to form a uniform solution. (A) Component: Specific copolymer that forms an alkali-soluble resin (B) Component: Fluorinated thermally decomposable polymer (C) Component: Solvent (D) Component: Photosensitizer (E) Component: Crosslinkable compound with two or more alkoxymethyl or hydroxymethyl groups (H) Component: Adhesion promoter

A positive-type photosensitive resin composition was prepared using the composition shown in Table 1. The composition ratios in Table 1 represent the ratios of solid components.

The positive-type photosensitive resin compositions of the Examples and Comparative Examples were used to form the first bank, and the upper film material 1 was used to form the second bank intersecting the first bank. The pattern shape during thermal curing was evaluated using the following method.

[Evaluation of Pattern Shape] Using a rotary coater, the positive-tone photosensitive resin compositions of the Examples and Comparative Examples were applied to an ITO-glass substrate. The coatings were then pre-baked on a hot plate at 110°C for 120 seconds to form films. These films were then irradiated with 365nm UV light at an intensity of 2.2mW/ ^cm² in the row direction through a mask patterned with lines (50μm) and spaces (160μm) for a predetermined time using a PLA-600FA UV irradiation device manufactured by CANON Co., Ltd. The films were then developed by immersing them in a 0.2% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds and then rinsed with ultrapure water for 30 seconds. The resulting coating was then post-baked at 230°C for 30 minutes to form a cured film with a thickness of approximately 0.5 μm, serving as the first bank. The top film material 1 was then applied to the resulting cured film using a rotary coater and pre-baked on a hot plate at 110°C for 120 seconds to form the coating. This coating was then irradiated with 365 nm UV light at an intensity of 2.2 mW/ ^cm² using a PLA-600FA UV irradiation device manufactured by CANON Co., Ltd., directed in the row direction through a mask patterned with lines (100 μm) and spaces (50 μm) for a predetermined period of time. Similarly, a cured film with a thickness of 0.9 μm was formed at the intersection of the first and second banks, serving as the second bank. The intersection of the first and second banks was 1.4 μm above the substrate. Using a Hitachi High-Technologies S-4800 field emission scanning electron microscope, the pattern shape was evaluated at the intersection of a 50 μm line pattern extending in the row direction and a 100 μm line pattern extending in the column direction.

Table 2 below shows the results of the above evaluation. As shown in Table 2, there is no significant difference in appearance between the pattern shapes formed by Example 1 and upper film material 1 and the pattern shapes formed by Comparative Example 3 and upper film material 1.

[Evaluation of Coating Properties] Next, for each of the photosensitive resin compositions obtained in Example 1 and Example 2 and Comparative Examples 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4, the coating properties on the Si wafer, the contact angle of the film after film formation (hereinafter referred to as Condition 1), the contact angle of the film formed after the development step (hereinafter referred to as Condition 2), and the contact angle of the film formed after the development step after UV/O ₃ irradiation (hereinafter referred to as Condition 3) were measured.

The photosensitive resin compositions of Examples and Comparative Examples were applied to Si wafers using a rotary coater and pre-baked on a hot plate for 120 seconds at 110°C to form a 1.1 μm thick photosensitive resin film. The resulting photosensitive resin film was visually inspected under a Na lamp and evaluated using the following criteria. No visible unevenness or streaking was rated (○), while visible unevenness or streaking was rated (×).

[Contact Angle Evaluation under Condition 1] The photosensitive resin compositions of Examples and Comparative Examples were applied to a Si wafer using a spin coater. The films were pre-baked on a hot plate at 110°C for 120 seconds to form a 1.1 μm thick photosensitive resin film. The films were then post-baked at 230°C for 30 minutes to form a 1.0 μm thick cured film. The contact angle of anisole on these cured films was measured using a contact angle meter (Drop Master) manufactured by Kyowa Interface Science Co., Ltd.

[Contact Angle Evaluation under Condition 2] The photosensitive resin compositions of Examples and Comparative Examples were applied to Si wafers using a spin coater and pre-baked on a hot plate for 120 seconds at 110°C to form a 1.1μm thick photosensitive resin film. The film was then immersed in a 0.4% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 90 seconds and then rinsed with ultrapure water for 20 seconds. The film was then post-baked at 230°C for 30 minutes to form a 1.0μm thick cured film. The contact angle of anisole on this cured film was measured using a Drop Master contact angle meter manufactured by Kyowa Interface Science Co., Ltd.

[Contact Angle Evaluation under Condition 3] The photosensitive resin compositions of Examples and Comparative Examples were applied to Si wafers using a spin coater and pre-baked on a hot plate for 120 seconds at 110°C to form a 1.1μm thick photosensitive resin film. The film was then immersed in a 0.4% by mass TMAH aqueous solution for 90 seconds and then rinsed with ultrapure water for 20 seconds. This was followed by post-baking at 230°C for 30 minutes to form a 1.0μm thick cured film. The film was then irradiated with UV light at 1.5J/ ^m² for a specified period of time using a UV-312 UV ozone cleaning system manufactured by Technovision Co., Ltd. The contact angle of anisole on the cured film was measured using a contact angle meter (Drop Master) manufactured by Kyowa Interface Science Co., Ltd.

The results are shown in Table 3 below.

As shown in Table 3, the Example exhibits excellent coatability, maintaining a contact angle of less than 5 degrees regardless of whether or not a development step or surface modification step is performed immediately after the cured film is formed. On the other hand, the Comparative Example exhibits excellent coatability, but its lyophilicity decreases immediately after the cured film is formed. While this improves during development due to the removal of the photosensitive resin film, the lyophilicity decreases after the surface modification step.

100: Structure 200: Structure 1, 2: Substrate 11, 12, 13, 14, 15, 16: First bank 21, 22, 23, 24, 25, 26, 27, 28: Second bank 15A: Region A of first bank 15 15B: Region B of first bank 15 16A: Region A of first bank 16 16A': Region A' of first bank 16 16B: Region B of first bank 16

Figure 1 is a perspective view of structure 100 having first and second banks formed therein. Figure 2 is a cross-sectional view of structure 100 taken along the A-A' line in Figure 1. Figure 3 is a perspective view of structure 200 having first and second banks formed therein. Figure 4 is a cross-sectional view of structure 200 in Figure 3, with (a) being a cross-sectional view taken along the B-B' line in Figure 3 and (b) being a schematic cross-sectional view taken along the C-C' line in Figure 3. Figure 5 is a plan view showing variations in the arrangement of the first and second banks. (a) shows a variation in which the height of the first bank from the substrate surface is varied, and (b) shows a variation in which the height of the first bank from the substrate surface is varied more complexly based on (a).

2:Substrate

12, 13, 14: First embankment

23,24: Second embankment

200:Construction

Claims (17)

A photosensitive resin composition is provided. The composition is suitable for use as a material for the first bank in a display device in which individual pixel areas are defined by providing first and second banks directly or via other layers on a substrate. The composition comprises the following components: (A) an alkali-soluble resin, (B) a fluorinated thermally decomposable polymer, (C) a solvent, (D) a photosensitizer, and (E) a crosslinking agent. The fluorinated thermally decomposable polymer of component (B) comprises a main chain (a) having a polymer structure of a polymerizable monomer and a side chain (b) having a functional group represented by the following general formula (1). (wherein, R ¹ , R ² , and R ³ are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, R ⁴ is a fluorinated alkyl group or a poly(perfluoroalkylene ether) chain; and Y ¹ is an oxygen atom or a sulfur atom.) The crosslinking agent of the component (E) is (E1) a crosslinking compound having two or more substituents selected from alkoxymethyl and hydroxymethyl groups, or (E2) a crosslinking compound selected from the crosslinking compounds represented by the following formula (2). (wherein k is an integer from 2 to 10, m is an integer from 0 to 4, and R is a k-valent organic group), the fluorinated thermally decomposable polymer is contained in an amount of 0.01 to 1 part by mass relative to 100 parts by mass of the alkali-soluble resin, and the crosslinking agent is contained in an amount of 1 to 50 parts by mass relative to 100 parts by mass of the alkali-soluble resin. The photosensitive resin composition of claim 1, wherein, on a substrate, the first bank is formed as: a structure adjacent to the second bank, and/or an isolated structure within an area surrounded by the second bank, and/or a structure intersecting the second bank; and further, the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface. The photosensitive resin composition of claim 1, wherein the second bank is formed on the substrate directly or via another layer above the first bank, and the height of the first bank from the substrate surface is lower than the height of the second bank from the substrate surface. The photosensitive resin composition of any one of claims 1 to 3, wherein R ⁴ is a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom. The photosensitive resin composition of any one of claims 1 to 3, wherein R ⁴ is a fluorinated alkyl group having 4 to 6 carbon atoms directly bonded to a fluorine atom. The photosensitive resin composition of any one of claims 1 to 3, wherein R ¹ , R ² , and R ³ are each independently a hydrogen atom, and R ⁴ is a fluorinated alkyl group having 1 to 6 carbon atoms directly bonded to a fluorine atom. The photosensitive resin composition of any one of claims 1 to 3, wherein the side chain (b) represented by the general formula (1) is represented by the following formula (1-1); A photosensitive resin composition according to any one of claims 1 to 3, wherein the photosensitive resin composition satisfies at least one of the following (Z2) to (Z4): (Z2): the alkali-soluble resin further has a self-crosslinking group, or further has a group reactive with at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, and an amino group; (Z3): the photosensitive agent is a photoradical generator and further contains, as component (F), a compound having two or more ethylenic double bonds; (Z4): the photosensitive agent is a photoacid generator and further contains, as component (G), a compound having two or more functional groups capable of forming covalent bonds with an acid generated from the photoacid generator. The photosensitive resin composition of any one of claims 1 to 3, wherein the photosensitizer is a quinone diazide compound. The photosensitive resin composition of claim 8, wherein the aforementioned photosensitive agent is a quinone diazide compound, further satisfies the aforementioned (Z2). The photosensitive resin composition of claim 10, wherein the aforementioned photosensitizer is naphthoquinone diazide. The photosensitive resin composition of any one of claims 1 to 3, wherein the number average molecular weight of the alkali-soluble resin is 2,000 to 50,000 in terms of polystyrene. The photosensitive resin composition of any one of claims 1 to 3, wherein in a display device having an organic thin film within the pixel area defined by the second bank and the first bank, the organic thin film is used in a pixel of an organic electroluminescent device. The photosensitive resin composition of any one of claims 1 to 3, wherein the aforementioned other layer is a hole injection layer of an organic electroluminescent device. A cured film formed by the photosensitive resin composition according to any one of claims 1 to 14. A display element having a hardened film as claimed in claim 15. A method for manufacturing a display device having a defined pixel area comprises: forming a first bank directly on a substrate or via another layer; and forming a second bank directly on the substrate or via another layer; the first bank being formed from the photosensitive resin composition of any one of claims 1 to 14.